Production of uranium tetrachloride



States PRODUCTION OF URANIUM TETRACHLORIDE No Drawing. Application-December 13, 1950 Serial No. 200,691.

9 Claims; (Cl. 23-145) My invention relates toan improved chlorination method and more particularly to the conversion of uranium values to UCl In various processes, large quantities of UCl are utilized as the starting material. In the course of such processes, certain waste uranium residues are collected from which the uranium is recovered in the form of such uranium values as UF UF, or uranium oxides. However, in orderto be suitable for return to the process :stream, these compounds must be converted to substantially pure UCL Considerable, difficulty has been encountered in effecting such conversions.

One of the more satisfactory processes that has thus far been developed for converting UF to UCL, comprises the multiple step process of dissolving UP in H O, add- :ing NH,OH, and digesting. to precipitate ammonium diuranate in accordance with U. S. Patent 2,466,118 issued April 5, 1949, separating the resulting precipitate, dissolving the precipitate in HNO and precipitating substantially all the dissolved. uranium as U by adding H 0 in the presence of aluminum ions, calcining, and chlorinating the resulting uranium oxide to UCL, by methods such as are described in co-pending patent applications Serial No. 737,156, filed March 25, 1947, now U. S. Patent No. 2,756,124, issued July 24, 1956; Serial No. 91,425, filed May 4, 1949, now U. S. Patent No. 2,688,529, issued September 7, 1954; and Serial No. 98,164, filed June 9, 1949, now U. S. Patent No. 2,688,530, issued September 7, 1954. These chlorination methods generally comprise treating a uranium oxide at elevated temperatures with chlorinating reagents such as CCL, or hexachlorpropylene.

Still other processes for converting UF to UCL; are disclosed in patent application Serial No. 659,853, filed April 5, 1946, now abandoned, and patent application Serial No. 182,134, filed August 29, 1950, now aban- :doned. These methods generally comprise reducing UP to UP, with reagents such as silicon tetrachloride, thionyl chloride, phosphorus trichloride and trichlorethylene. The resulting UR, is then converted to the desired UCL, by calcining to a uranium oxide and subsequently chlorinating to UCl, as already indicated above.

It is noted that at least three major steps are required in the prior art to effect conversion from UF to UCl with a uranium oxide constituting an intermediate compound in these processes.

An object of my invention is to provide a suitable process for the production of UCL; from uranium values.

A further object is to provide an improved, shorter process for the production of UCL, from UF Another object is to provide an improved process for the production of UCl, from UP; and uranium oxides.

Additional objects and advantages of the present invention will appear from the following description.

In accordance with the present invention, UP may be converted to UCld, by converting the UP to UP, or U0 as described in the prior art, and the resulting UR, and/ or 2,864,566 Patented Dec. 16, 1958 ice U0 may be transformed directly to UCl, by contacting the UP, and/ or U0 with relatively low melting inorganic chlorides such as AlCl BCl or NaAlCl, under substantially anhydrous conditions, in liquid-solid or vapor-solid states, and recovering the resulting UCL, from the resulting mixture by any suitable methods.

My method is particularly advantageousfor the direct chlorination of UP, and U0 to form UCl, of generally satisfactory purity. However, tetravalent uranium compounds, in general, may satisfactorily be utilized in like manner." In addition, easily reducible hexavalent uranium compounds, such as UF may be directly treated with the herein disclosed chlorinating agents to form UCl UF; readily being converted to'UF and the resulting UP, converted to UCl in accordance with my invention, by the remaining excess of chlorinating agent.

Other compounds containing uranium of valence greater than four may be converted to UCl in accordance with my invention, but usually in relatively low yields. However, these yields may be considerably improved by reducing these compounds before chlorination, or by including a reducing agent in the chlorination reactions herein disclosed.

Since uranium oxides are readily available and uranium oxides other than U0 may be easily convertedto U0 by conventional methods, and since U1 is a special problem in certain plant wastes in view of its extreme insolubility and general lack of reactivity, I will further illustrate my invention specifically with respect to UR; and U0 Reactive uranium dioxide can be obtained,.for example, by reduction of the higher oxides with methane, ammonia or ethanol below 750 C.; or by thermal decomposition of uranium (IV) compounds such as the sulfate, oxalate or benzoate. Uranium dioxide obtained in this way is a grey-black, pyrophoric powder which oxidizes rapidly in air. The coffee-brown dioxide prepared by reduction or thermal decomposition above 800 C. is much more inert.

My invention can be carried out either by a vapor-solid reaction in which a vaporized chlorinating agent is passed over a solid uranium compound at elevated temperatures or by a liquid-solid reaction at more moderate tempera tures, in which the molten chlorinating agent is mixed with the solid uranium compound.

The temperature of any of the disclosed reactions is not critical, but rather is dependent upon the melting point or vaporization temperature of the specific chlorinating agent being utilized. Thus, if, in accordance with my invention, it is desired to effect a liquid-solid reaction, a temperature sufficiently high to melt the chlorinating agent must be utilized and correspondingly, a temperature sufficiently high to vaporize the chlorinating agent must be utilized to effect a vapor-solid chlorination reaction.

Only a slight excess over the stoichiometric quantity of chlorinating agent need be utilized in effecting the liquid-solid reactions, whereas, a considerable excess may be required for the vapor-solid reactions. However, in the latter, the excess is readily recoverable from the reaction products as described hereinafter.

Two general procedures are found satisfactory for carrying out these reactions. In one, the uranium values are placed in a vessel adapted to pressure and vacuum operation. The inorganic chlorinating agent is introduced and the vessel evacuated. The system is then heated until the chlorinating agent melts. Agitation may then be applied for a short period. After only a few minutes, the reaction appears to be complete, the reaction products remaining in the reaction mixture, However, approximately 15 rninutes reaction time is preferred in order to assure an optimum yield. This method is crushed and subjected to a fractional distillation. fremaining AlCl volatilized at about 200 C., the UCI.

3 particularly suitable when AlCl is the chlorinating agent. When NaAlCL, is the chlorinating agent, a pressure vessel need not be utilized, but approximately 30% excess of AlCl by weight should be added to the molten liquid to offset the loss of AlCl by sublimation at the reaction temperature.

In another method, the chlorinating agent in the vapor state is p-assedover the solid uranium compound in a tube-like reactor at a temperature at least higher than the volatilization temperature of UCL; until substantially all the .uranium compound is transformed intoUCL Excess chlorinating reagent and the resulting UCl vapor may be condensed in a far section of the tube reactor and reheated to effect adistillatio n separation of the condensed material, the excess chlorinating agent being easily trapped for reuse. AlCl and BCI are particularly suited for this method, BCl providing the extra advantage of producting no reaction products which are solids at the reaction temperature. My invention will be further illustrated by the following specific examples.

Example I to III illustrate unsuccessful attempts to produce UCl from UF Example I Two grams of UR; were triturated with 4 grams sugar charcoal and heated to 300 under nitrogen. Chlorine was then passed through the system and the temperature raised to 600-650. Most of the brown-red volatile product obtained appeared by analysis to be a mixture of UCl and UCl F.

Example 11 Ten grams of UR; were placed in 20 ml. SiCl in a steel bomb, the bomb then being chilled in liquid oxygen and the system evacuated. Even after heating the bomb to 243 the reactants appeared unchanged, no evidence being present for the formation of any UCl and the green solid remaining still analyzed as UF Example III Example IV The following procedure for a liquid-solid reaction, using AlCl to convert UF to UCl was utilized:

Since AlCl does not melt but sublimes at atmospheric pressure, this procedure was conducted in a bomb type reactor. Approximately 27 grams of UF and about 40 grams of anhydrous AlCl were placed in a 50 cc. reactor which was chilled, subjected to vacuum and sealed off. Then the reactor was heated in an oil bath, to 215- 230 C. until the AlCl melted under its own pressure.

A very dark but clear green solution resulted. After the solution had cooled and solidified, the resulting solid was i The product sublimed at about 650 C., and the A11 byproduct remained behind as a relatively non-volatile residue.

1: 1) and heated gradually until a molten liquid (NaAlCl formed between 185200 C. Approximately 20 grams "excess of MCI; were-then added tothe molten liquid to' offset the gradual loss of A101 vapor while the tem- I invention, would be one which gives rise only to volatile v perature of the liquid was increased to about 300 C. 25 grams of solidUF was then added to the liquid, the blue- -green UF changing rapidly into a dark green salt, most of which settled out of solution. The molten liquid was decanted off from the dark green residue, the residue by analysis was substantially pure U01 contaminated slightly by occluded NaAlCl Example VI The procedure of Example V was followed except that U0 was added to the molten liquid instead of UF The product was substantially pure UC1 Example VII A procedure for a vapor-solid reaction using A101 for converting UF to UCl; was as follows:

Purified nitrogen was passed over AlCl at 300 C. and the resulting diluted AlCl vapor was passed over solid UF at 600 to 650 C. in a Vicor tube reactor. Both AlCl and a green crystalline product condensed on the cool end of the Vicor tube. The condensed material was then heated at 350 C. and the AlCl sublimed ofl leaving the green crystalline substance behind. Upon analysis, the green colored product proved to be U01 It may be noted that the excess AlCl used in this reaction can be easily trapped and used again.

On a small scale, i. e., about 5 to 10 grams U1 with excess AlCl this process proved very effective. However, some difficulty might be encountered in large scale operations, for non-volatile A11 is formed during the reaction and might tend to'form a coating over the hitherto unreacted UF ,'thus impeding further reaction of the tetrafluoride with AlCl This difiiculty may be circumvented by using thin layers of UF or by using a rotating reactor tube.

The ideal chlorinating agent, in accordance with our reaction products, thus simultaneously increasing the reaction rate. chlorinating agent. 7 Example VIII Extremely pure BCl was passed over five grams of UF at 600 C. until allthe UF had reacted with the BCl to form volatile products. Pure UC1 was separated from the reaction products by selective condensation, the remaining BCl and the resulting BF being considerably more volatile.

It is to be understood, of course, that the above examples are merely illustrative, and do not limit the scope of our invention. Other inorganic chlorinating agents and other reaction conditions may be substituted for those of the examples, in accordance with the foregoing disclosure. We find, in general, that inorganic chlorides capable of acting as either polar or non-polar substances, depending upon the circumstances .involved, may be utilized in accordance with our invention to effect satisfactory conversion of uranium values to UCl Thus, in general, it may be said that the use of any equivalents or modifications of procedure which would naturally occur to those skilled in the art is included in the scope of the present invention. Only such limitations should be imposed on the scope of our invention as are indicated in the appended claims.

What is claimed is:

l. A process for the production of UCL, which comprises contacting uranium values under substantially an- The following example illustrates such a 2. The process of claim 1 in which the uranium values are uranium fluorides.

3. The process of claim 1 in which the uranium values are U0 4. The process of claim 1 in which the chlorinating agent is AlCl and the temperature and pressure are such that the AlCl is maintained in the molten state.

5. The process of claim 1 in which the chlorinating agent is NaAlCL; and the temperature and pressure are such that the NaAlCL, is maintained in the molten state.

6. The process of claim 1 in which the chlorinating agent is AlC1 and the temperature is such that the AlCl is maintained in the vapor state.

7. The process of claim 1 in which the chlorinating agent is BCl and the temperature and pressure are such that the BCl is maintained in the molten state.

8. The process of claim 1 in which the chlorinating agent is BCl and the temperature is such that the BCl is maintained in the vapor state.

9. A process for the production of UCl which comprises contacting uranium fluoride under substantially anhydrous conditions with BCl at a temperature and pressure such that said BCl is maintained in the vapor state until said uranium fluoride is substantially completely converted to UCL; and thereafter recovering UCL; from the resulting reaction products.

References Cited in the file of this patent 

1. A PROCESS FOR THE PRODUCTION OF UCL4 WHICH COMPRISES CONTACTING URANIUM VALUES UNDER SUBSTANTIALLY ANHYDROUS CONDITIONS WITH AT LEAST ONE INORGANIC CHLORIDE SELECTED FROM THE GROUP OF INORGANIC CHLORIDES CONSISTING OF ALCL3, BCL3 AND NAALCL4 AT A TEMPERTURE AND PRESSURE SUCH THAT SAID CHLORIDES ARE MAINTAINED IN AT LEAST THE MOLTEN FORM, UNTIL SAID URANIUM VALUES ARE SUBSTANTIALLY COMPLETELY CONVERTED TO UCL4 AND THERAFTER RECONVERTRING UCL4 FROM THE RESULTING REACTION PRODUCTS. 